Phase transitions of a single polymer chain: A Wang-Landau simulation study

A single flexible homopolymer chain can assume a variety of conformations which can be broadly classified as expanded coil, collapsed globule, and compact crystallite. Here we study transitions between these conformational states for an interaction-site polymer chain comprised of N = 128 square-well-sphere monomers with hard-sphere diameter sigma and square-well diameter lambda sigma. Wang-Landau sampling with bond-rebridging Monte Carlo moves is used to compute the density of states for this chain and both canonical and microcanonical analyses are used to identify and characterize phase transitions in this finite size system. The temperature-interaction range (i.e., T-lambda) phase diagram is constructed for lambda <= 1.30. Chains assume an expanded coil conformation at high temperatures and a crystallite structure at low temperatures. For lambda > 1.06 these two states are separated by an intervening collapsed globule phase and thus, with decreasing temperature a chain undergoes a continuous coil-globule (collapse) transition followed by a discontinuous globule-crystal (freezing) transition. For well diameters lambda < 1.06 the collapse transition is pre-empted by the freezing transition and thus there is a direct first-order coil-crystal phase transition. These results confirm the recent prediction, based on a lattice polymer model, that a collapsed globule state is unstable with respect to a solid phase for flexible polymers with sufficiently short-range monomer-monomer interactions. (C) 2009 American Institute of Physics. [doi: 10.1063/1.3227751]